JP2847419B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly, to a silver halide photographic material having high sensitivity, low residual color contamination, and excellent stagnant stability. It relates to a photosensitive material.

[Background of the Invention]

In recent years, high sensitivity, high image quality, and improvement in manufacturing suitability of silver halide photographic materials have been demanded from various viewpoints.
For this reason, improvement research is being conducted in various fields.

In order to expand the photosensitive wavelength range inherent in silver halide emulsions and spectrally sensitize it to the visible light range, which originally has no sensitivity,
The use of specific sensitizing dyes is well known.

The sensitizing dye used for the above purpose has high sensitivity, causes less staining of the dye after processing, and is stored in an insulated state after adding the sensitizing dye to the emulsion and coating. In this case, a change in the sensitivity (hereinafter referred to as stagnation stability) is selected.

As such spectral sensitizing dyes, certain pentamethine dyes used in red-sensitive emulsions are known to be very effective, but sensitizing dyes that simultaneously satisfy the above demands are not known. This is the actual situation.

In view of such a situation, the present inventors have assiduously studied and, as a result, have satisfied the above demand by introducing an alkyne derivative into the sensitizing dye, that is, a sensitizing dye having high sensitivity, high image quality, and excellent production suitability. Invented the invention.

As a sensitizing dye into which an alkyne derivative has been introduced, a dye disclosed in US Pat. No. 4,375,508 is known. The patent discloses an example of a carbocyanine dye substituted with a substituted alkyne on a nitrogen atom.However, when this is applied to a dicarbocyanine dye, sensitivity, stagnation safety is not satisfactory, Improvement was desired. Further, this patent aims at improving the water solubility, and therefore, it is required that the substituent on the nitrogen atom is a substituted alkyl, and it is particularly desirable that the acid group is substituted. On the other hand, in the present invention, the alkyne moiety has a hydrogen atom and does not have a substituent other than the binding part to the dye, so that the technical idea and the configuration are different from the patent. It is.

[Object of the invention]

Therefore, an object of the present invention is to contain a novel pentamethine dye sensitizing the red region, high sensitivity and little dye contamination,
Another object of the present invention is to provide a silver halide photographic material having improved stagnation safety.

[Configuration of the invention]

In view of the above problems, the present inventors have conducted intensive studies, and as a result, the object of the present invention is to provide a silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on a support, wherein the silver halide emulsion It has been found that a silver halide photographic material is characterized in that at least one of the layers contains silver halide grains spectrally sensitized by at least one of the dyes represented by the following general formula [I]. .

 General formula [I] Where R₁Is an alkyl group or -J_Two-C≡CH, J₁
And J_TwoRepresents a divalent linking group. R_Two, R_Three, R_Four, R_Five, R₆, R₇,
R₈, R₉Is hydrogen atom, alkyl group, aryl group, halogen
Atom, represents an alkoxy group, R_Two~ R_FiveAnd R₆~ R₉Is
A ring may be formed in cooperation with each adjacent substituent.
Z is a group of hydrocarbon atoms necessary to form a 5- or 6-membered ring
Represents X Represents an acid anion. l represents 0 or 1
You.

 Hereinafter, the present invention will be described in more detail.

In the general formula [I], examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2-methoxymethyl group, a 2-methoxyethyl group, a 3-methoxybutyl group, and a 4-methoxybutyl. Group, 3
-Methoxypropyl group, 2-ethoxyethyl group, 1-methoxymethylpropyl group, 3-methoxy-3-methylbutyl group, 1-methyl-2-methoxyethyl group, 3-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxy Ethyl group, o-methoxybenzyl group, m-methoxybenzyl group, p-methoxybenzyl group, o-methoxyphenethyl group, o-ethoxybenzyl group, p-ethoxybenzyl group, p-methoxyphenethyl group, p-hydroxy-m -Methoxybenzyl group, 4- (4-methoxyphenethyl) butyl group, 2- (4-methoxyphenyl)
-1-methylethyl group, 3- (4-methoxyphenyl)
A propyl group and a 4-ethoxy-3-methoxybenzyl group.

j ₁ and j ₂ are each independently a divalent linking group, for example, a hydrocarbon group such as methylene, ethylene, propylene, 2-methylpropylene, a group in which a part of a carbon chain is replaced by an oxygen atom, —CONR ₁₁ − , -CO-, -CR ₁₂ R ₁₃ CO-, Represents

(However, R _{11 to} R ₁₅ represent a hydrogen atom, an alkyl group, or an aryl group. L ₂ and m ₂ each represent an integer of 4 or less.) R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group,
Isopropyl, butyl, (t) butyl, methoxyethyl, 3-ethoxybutyl, 4-methoxybutyl, synunomethyl, phenylmethyl, hydroxymethyl, chloromethyl, and the like; For example, a phenyl group, a toluyl group, a p-chlorophenyl group and the like can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom, and examples of the alkoxy group include a methoxy group, an ethoxy group and a methoxyethoxy group. These may form a ring in cooperation with each other.For example, R ₄ and R ₅ may form a benzene ring, R ₇ and R ₈ may form a cyclohexene ring, and R ₃ and R ₄ may form a dioxirane ring. it can.

Examples of the 5-membered hydrocarbon ring formed by Z include a 2-cyclopentene ring, and the like.
Examples thereof include a 5,5-dimethyl-2-cyclohexene ring and a 4,4,6,6-tetrameethyl-2-cyclohexene ring.

 X Is an acid anion, specifically a halogen ion (eg,
For example, chlorine ion, bromine ion, iodine ion, etc.), p-to
Ruene sulfonate ion, perchlorate ion,
Iodine ions and the like can be mentioned. Set the charge of the whole molecule to 0
Thus, l represents 0 or 1 as appropriate.

 Next, a preferred embodiment of the present invention will be described.

In the general formula [I], preferably, Z is And more preferably R ₃ , R ₄ ,
R ₇ and R ₈ are all hydrogen, most preferably in addition to this condition, when J ₁ is methylene.

Specific examples of the sensitizing dye represented by the general formula [I] are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

The sensitizing dye represented by the general formula [I] is described in, for example, "The Chemistry of Heterocyclic Compounds" by FM Hammer.
cyclic Compounds), Volume 18, "The Cyanine Soybean
And Related Compounds "(The Cyanine
Dyes and Related Compounds) (A. Weissherger ed. Int
erscience, New York 1964). Next, representative examples will be described.

(Synthesis of Exemplified Compound 6) (1) Synthesis of 2-methyl-3-propargylbenzthiazolium bromide.

1.49 g of 2-methylbenzthiazole and 2.38 g of propargyl bromide were dissolved in 3.9 g of m-cresol, and 12
After reacting for an hour, the mixture is left to cool, 50 ml of ethyl acetate is added, and the precipitated crystals are collected by filtration, washed with ethyl acetate and dried.

 Yield 1.95 g (50.4%) mp 220 ° C. (discolored above 190 ° C.) The maximum absorption in methanol was confirmed at 425 nm by NMR and mass spectrum.

(2) Synthesis of 2- (3,5,5-trimethyl-2-cyclohexene-1-ylidenemethyl) -3-propargyl-benzothiazolium bromide.

2-methyl-3-propargylbenzthiazolium bromide 1.88 g, isophorone 1.36, ammonium acetate 0.2
After refluxing 7 g in 3.1 g of glacial acetic acid for 1.5 hours, the mixture was heated for 3 hours while distilling off the solvent at normal pressure, and the solvent was removed by distillation under reduced pressure to 30 mmHg. After standing to cool, chloroform is added with 10 ml of water.
After washing twice, the chloroform layer is dried over anhydrous magnesium sulfate, and the solvent is removed. Add 30 ml of ethyl acetate, stir and crystallize. The precipitated crystals are collected by filtration, washed with ethyl acetate and dried.

 Yield 1.0 g (36.8%) The structure was confirmed by NMR and mass spectrum.

(3) Synthesis of Exemplified Compound 6.

2- (3,5,5-trimethyl-2-cyclohexene-1
-Ylidenemethyl) -3-propargyl-benzothiazolium bromide (0.97 g) and 2- (2-methoxyethyl)
While stirring 1.37 g of -3- (2-methoxyethyl) -benzthiazolium paratoluenesulfonate in 4 ml of acetonitrile, 0.38 g of triethylamine was added. After reacting at room temperature for 5 hours, 20 ml of ethyl acetate was added,
The precipitated crystals are collected by filtration. Recrystallization from alcohol gave blue crystals.

 Yield 0.54 g (32%) The structure was confirmed by an absorption maximum 645 nm NMR and mass spectrum in methanol.

The optimum amount of the sensitizing dye represented by the general formula [I] can be determined by a method known to those skilled in the art. For example,
There is a method in which a certain emulsion is divided, sensitizing dyes having different concentrations are contained in the respective emulsions, and the performance is determined by measuring the performance of each emulsion.

The addition amount of the sensitizing dye in the present invention is not particularly limited, but may be 2 × 10 ⁻⁶ mol to 1 × 10 ⁻² per mol of silver halide.
It is preferable to use a mole, more preferably 5 × 10 ⁻⁶ mole to 5 ×
It is preferred to use 10 ^-3 mol.

For the addition of the sensitizing dye to the emulsion, a method well known in the art can be used. For example, these sensitizing dyes can be directly dispersed in the emulsion, or dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, or a mixture thereof, or diluted with water. Or dissolved in water and added to the emulsion in the form of these solutions. Ultrasonic vibration can be used during the dissolution process.
As described in U.S. Pat.No. 3,469,987, a method in which a dye is dissolved in a volatile organic solvent, this solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion, As described in JP-A-42185 or the like, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion is also used. The dye can be added to the emulsion in the form of a dispersion by an acid dissolution dispersion method. For addition to the emulsion, the methods described in U.S. Pat. Nos. 2,912,435, 3,342,605, 2,996,287 and 3,425,835 can also be used. The sensitizing dye represented by the general formula [I] can be added to the emulsion at any time during the production process from the time when silver halide grains are formed until immediately before coating on a support. .

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, from the end of the formation of silver halide grains to the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, during chemical sensitization, It can be added at any time selected from the time of completion and from the end of chemical sensitization to the time of coating. Addition is 1
It may be carried out once or in a plurality of times. The sensitizing dye represented by the general formula [I] can be used as a so-called supersensitizing combination in combination with other sensitizing dyes. In this case, each sensitizing dye may be dissolved in the same or different solvent, and these solutions may be mixed or added separately to the emulsion prior to addition to the emulsion. When they are added separately, their order and time interval can be arbitrarily determined according to the purpose.

As the sensitizing dye used in the present invention, a higher spectral sensitivity can be obtained by using a compound having a supersensitizing effect in combination.

Compounds having such a supersensitizing effect include, for example, U.S. Pat. Nos. 2,933,390, 3,416,927, and 3,511,664.
No. 3,615,613, 3,615,623, 3,635,721, etc., each having a pyrimidylamino group or a triazinylamino group, a compound having an aromatic organic formaldehyde described in British Patent No. 1,137,580, U.S.A. Patent
4,030,927, halogenated benzotriazole derivatives, JP-A-59-142541, bis-pyridinium compounds described in JP-A-59-188641, and aromatic heterocyclic quaternary salts described in JP-A-59-191032 Compound, JP-A-60-79348
Patent Document No. 4; electron-donating compound; U.S. Pat.No. 4,307,183, a polymer containing an aminoallylidenemalononitrile unit described in U.S. Pat.No. 4,307,183; hydroxytetrazaindene derivative described in JP-A-55-149937; U.S. Pat. Described 1,3-oxadiazole derivative, U.S. Patent 4,780,404
And amino-1,2,3,4-thiatriazole derivatives described in the specification.

The timing of adding these supersensitizers is not particularly limited, and they can be arbitrarily added according to the timing of adding the sensitizing dye. The addition amount is selected in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol per mol of silver halide, and the sensitizing dye is used at an addition molar ratio of 1/1 to 10/1.

The sensitizing dye of the present invention is preferably used in combination with a phenol resin having a repeating unit represented by the following general formula [II] from the viewpoint of sensitivity and raw sample preservability.

General formula (II) Wherein R ₃ is a hydrogen atom, a halogen atom, an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, alkoxy group, hydroxyl group, amino group, acyl group or -SO
₂ represents a R ₅ group, and R ₅ represents a hydroxyl group, an alkoxy group, an alkyl group, an aryl group, an amino group or a hydrazino group.

R ₄ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. m represents an integer of 0 to 3. The silver halide grains contained in the silver halide emulsion layer according to the present invention may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide. May be mixed. Among them, silver chloride-containing emulsions are more preferable.

The composition of the silver halide grains used in the present invention may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the composition inside and outside the particles is different, the composition may change continuously or may change discontinuously.

The particle size of the silver halide grains used in the present invention is not particularly limited, but in consideration of sensitivity and other photographic performance, etc.
Preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm
m.

The particle size can be measured by various methods generally used in the art.

Typical methods include Lapland's "Analysis of Particle Size" ASTM Symposium on Right Microcopy, 1955, pp. 94-122 or "Theory of Photographic Processing"
It is described in Chapter 2 of Mies and James, Third Edition, published by Macmillan, Inc. (1966).

The particle diameter is calculated using the projected area of the particle or a direct approximation.
This can be measured.

If the particles are substantially uniform in shape, the particle distribution can represent this fairly accurately as a diameter or projected area.

In the present invention, the particle size distribution of the silver halide grains may be polydisperse or monodisperse, but is preferably a monodisperse emulsion. More preferably, the silver halide grains are monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 0.10 or less, in the particle size distribution.

Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri is the particle size of each particle, ni is the number of particles having the particle size of ri, and the particle size here is the diameter of spherical silver halide particles, and also the diameter other than cubic or spherical. In the case of a particle having a shape, the diameter represents a diameter when the projected image is converted into a circular image having the same area.

The silver halide grains used in the present invention may be obtained by any of an acidic method, a neutral method, and an ammoniacal method. The particles may be grown at one time, or may be grown after seed particles have been made.

The method of producing the seed particles and the method of growing may be the same or different.

The form in which the soluble silver salt and the soluble halogen salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferable. Further, as one form of the simultaneous mixing method,
The pAg-controlled double jet method described in 48521 and the like can be used.

If necessary, a silver halide solvent such as thioether may be used.

Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide grains according to the present invention can be formed by any method.

One preferable example is a cube having a {100} plane as a crystal surface. U.S. Pat.Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42737, etc., and "The Journal of Photographic Science" (J.photogr.Sci.), 21, 39 (1973), etc. According to the method described in the above document, particles having shapes such as an octahedron, a tetrahedron, and a dodecahedron can be produced and used.

 Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains used in the present invention may be a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex wire thereof during a grain forming process and / or a growing process.
Metal ions can be added using rhodium salts or complex salts thereof, iron or complex salts thereof, and can be contained inside the particles and / or on the surface of the particles. And / or a reduction sensitization nucleus can be provided on the surface of the grains.

The inclusion of the iridium salt or its complex salt inside the particles and / or on the surface of the particles is preferable in that the failure property at the time of exposure is improved.

In the present invention, after the growth of the silver halide grains is completed, unnecessary soluble salts may be removed or may be kept contained.

The removal of the salts can be carried out according to Research Disclosure No. 17643.

The silver halide grains used in the present invention may be grains whose latent image is mainly formed on the surface, or grains whose latent image is mainly formed inside the grain. Preferably, the latent image is a particle mainly formed on the surface.

In the present invention, a chemical sensitizer, for example, a chalcogen sensitizer can be used. Chalcogen sensitizer is a general term for sulfur sensitizer, selenium sensitizer, tellurium sensitizer,
For photographic use, a sulfur sensitizer and a selenium sensitizer are preferred.

Known sulfur sensitizers can be used. For example, thiosulfate, allyl thiocarbazide, thiourea, allyl isothiocyanate, cystine p-toluene thiosulfonate, rhodanine are mentioned. Others
U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947
No. 2,728,668, 3,501,313, 3,656,955,
West German Application Publication (OLS) No. 1,422,869, JP-A-56-24937
And the sulfur sensitizers described in JP-A-55-45016 and the like can also be used.

The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature, and the size of silver halide grains, but the standard is 10 ^-7 per mol of silver halide.
Mol to 10 ^-1 mol is preferred.

A selenium sensitizer can be used instead of the sulfur sensitizer. Examples of the selenium sensitizer include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, and selenocarbon. Acid salts and esters, selenophosphates, diethyl selenide, diethyl selenide selenides can be used, and specific examples thereof are described in U.S. Pat.
Nos. 4,944, 1,602,592, and 1,623,499. Further, reduction sensitization can be used in combination. The reducing agent is not particularly limited, but includes known stannous chloride, thiourea dioxide, hydrazine, polyamine and the like. Also, noble metal compounds such as platinum compounds and palladium compounds can be used.

As the gold sensitizer, the oxidation number of gold may be +1 or +3, and other kinds of gold compounds may be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold salafide, gold selenide, etc. No.

The amount of the gold sensitizer to be added varies depending on various conditions, but as a guide, it is from 10 ^-8 mol to 10 ^-1 mol, preferably from 10 ^-7 mol to 10 ^-2 mol, per mol of silver halide. These compounds may be added at any time during the formation of silver halide grains, during physical ripening, during chemical ripening, or after the completion of chemical ripening.

When a gold compound is used in the present invention, a light-sensitive material having better raw sample preservability can be obtained.

In the present invention, the silver halide emulsion is subjected to chemical sensitization during chemical sensitization during the production process of the photographic material, during storage or during photographic processing, and / or for the purpose of keeping the photographic performance stable. At the end, at least one point after the end of the chemical sensitization and before coating the silver halide emulsion, compounds known as antifoggants or stabilizers in the photographic industry can be added.

Examples of the stabilizer that can be used in the present invention include, for example, tetrazaindene compounds such as 7-hydroxy-5-methyl-1,3,4,7a-tetrazaindene.

In the present invention, an inhibitor that is effectively used has a solubility product (Ksp) with silver ion of 1 × 10 ⁻¹⁰ or less, preferably Ksp.
Is 1 × 10 ⁻¹¹ or less. A compound having a solubility product exceeding this, that is, a compound having a lower ability to form a salt with silver ions, cannot provide the desired effect.

For measuring and calculating the solubility product, "New Experimental Chemistry Course 1"
(Maruzen), pages 233 to 250 can be referred to.

Examples of the inhibitor include “Chemical and Pharmaceutical Beurethane” (Chemical and Pha
rmaceutical Bulletin) (Tokyo) 26, 314 (1978),
Japanese Patent Application Laid-Open No. 55-79436, "Berichte del Deutschen Chemischen Geisels draft" (Berichte and
Deutschen Chemischen Gesellsdraft) 82,121 (194
8), U.S. Patent Nos. 2,843,491, 3,017,270, UK Patent 9
40,169, JP-A-51-102639, `` Journal of
American Chemical Society, 44, 1502-1510,
"Beilsteins Handbuchder Organisch"
en Chemie) 26 , 41, 43, 58, etc.
The synthesis can also be performed according to the methods described in these documents.

When the present invention is applied to a color light-sensitive material, various dye-forming substances are used, and a typical one is a dye-forming coupler.

As the yellow dye-forming coupler, various acylacetanilide-type couplers can be preferably used. Of these, benzoylacetoanilide and pivaloylacetoanilide compounds are advantageous.

Specific examples of yellow couplers that can be used are described in British Patent 1,07
No. 7,874, JP-B-45-40757, JP-A-47-1031, 47
-26133, 48-94432, 50-87650, 51-363
No. 61, No. 52-115219, No. 54-99433, No. 54-133329
Nos. 56-30127, U.S. Pat.Nos. 2,875,057 and 3,253,92
No. 4, 3,265,506, No. 3,408,194, No. 3,551,155, No.
3,551,156, 3,664,841, 3,725,072, 3,73
0,722, 3,891,445, 3,900,483, 3,929,484
No. 3,933,500, No. 3,973,968, No. 3,990,896,
No. 4,012,259, No. 4,022,620, No. 4,029,508, No. 4,0
57,432, 4,106,942, 4,133,859, 4,269,93
No. 6, 4,286,053, 4,304,845, 4,314,023,
4,336,327, 4,356,258, 4,386,155, 4,4
Also, those described in No. 01,752.

The diffusion-resistant yellow coupler used in the light-sensitive material of the present invention is preferably represented by the following general formula [Y].

General formula [Y] In the formula, R ₁ represents a halogen atom or an alkoxy group.

R ₂ represents a hydrogen atom, a halogen atom or an optionally substituted alkoxy group.

R ₃ may have a substituent, an acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group, or Represents an aryloxy group.

Z ₁ represents a group capable of leaving upon coupling with an oxidized form of the color developing agent.

In the present invention, couplers represented by the following general formulas [a] and [aI] can be preferably used as magenta dye image forming couplers.

General formula [a] [In the formula, Ar represents an aryl group, Ra1 represents a hydrogen atom or a substituent, and Ra2 represents a substituent. Y represents a hydrogen atom or a substituent which can be eliminated by reaction with an oxidized form of a color developing agent, and W represents -NH-, -NHCO- (N atom is bonded to a carbon atom of a pyrabilone nucleus) or -NHCONH-. , M is 1 or 2
It is. Preferred examples of the compound represented by the general formula [a] are as follows.

General formula (a I) [In the formula, Za represents a group of nonmetal atoms necessary to form a nitrogen-containing heterocyclic ring, the ring formed by Za may have a substituent, X is a hydrogen atom or a color developing agent. It represents a substituent which can be eliminated by a reaction with an oxidant. Ra represents a hydrogen atom or a substituent. As the substituent represented by Ra, for example, a halogen atom,
Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocyclic, acyl, sulfonyl, sulfinyl, phosphonyl, carbamoyl, carbamoyl, sulfamoyl, cyano, spiro compound residues, Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic group oxy group, siloxy group, acyloxy group, albamoyl group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino Group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples include an alkylthio group, an arylthio group, and a heterocyclic thio group.

These are, for example, U.S. Pat.Nos. 2,600,788 and 3,061,432.
Nos. 3,062,653, 3,127,269, 3,311,476,
3,152,896, 3,419,391, 3,519,429, 3,5
No. 55,318, No. 3,682,514, No. 3,888,680, No. 3,907,57
No. 1, No. 3,928,044, No. 3,930,861, No. 3,930,866,
Nos. 3,933,500, JP-A-49-29639 and JP-A-49-29639.
No. 111631, No. 49-129538, No. 50-13041, No. 52-589
No. 22, No. 53-62454, No. 55-118034, No. 56-38043
Nos. 57-35858 and 60-23855, UK patents
Nos. 1,247,493, Belgian Patent Nos. 769,116, 792,525, German German Patent Nos. 2,156,111, JP-B-46-60479, JP-A-59-125732, JP-A-59-228252, JP-A-59-162548,
These are described in JP-A Nos. 59-171956, 60-33552, and 60-43659, West German Patent 1,070,030, and U.S. Pat. No. 3,725,067.

Hereinafter, typical specific examples of the magenta coupler represented by the general formula [aI] used in the present invention will be described, but these are merely examples, and the present invention is not limited thereto.

Representative examples of cyan dye image forming couplers include phenol-based and naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming couplers, and are described in US Pat. No. 2,306,410.
No. 2,356,475, 2,362,598, 2,367,531,
No. 2,369,929, No. 2,423,730, No. 2,474,239, No. 2,4
76,008, 2,498,466, 2,545,687, 2,728,66
No. 0, 2,772,162, 2,895,826, 2,976,146,
No. 3,002,836, No. 3,419,390, No. 3,446,622, No. 3,4
No. 76,563, No. 3,737,316, No. 3,758,308, No. 3,839,04
No. 4, UK Patent Nos. 478,991, 945,542, 1,084,480, 1,377,233, 1,388,024 and 1,543,040, and JP-A-47-37425 and JP-A-50-10135.
No. 50-25228, No. 50-112038, No. 50-117422
No. 50-130441, No. 51-6551, No. 51-37647,
No. 51-52828, No. 51-108841, No. 53-109630, No. 5
4-48237, 54-66129, 54-131931, 55-3
Nos. 2071, 59-146050, 59-31953 and 60-117
No. 249.

As the cyan image forming coupler, the following general formula [E]
Alternatively, a coupler represented by [F] can be preferably used.

General formula [E] In the formula, R _1E represents an aryl group, a cycloalkyl group or a heterocyclic group. R _2E represents an alkyl group, an aryl group, a cycloalkyl group or a heterocyclic group.

R _2E represents an alkyl group or a phenyl group.

R _3E represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Z _1E represents a hydrogen atom, a halogen atom, or a group which can be eliminated by a reaction with an oxidized aromatic primary amine color developing agent.

General formula [F] In the formula, R _4F represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a nonyl group, and the like). R _5F
Represents an alkyl group (for example, a methyl group, an ethyl group, etc.).
R _6F represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group (eg, methyl group, ethyl group, etc.). Z _2F represents a hydrogen atom, a halogen atom or a group which can be eliminated by a reaction with an oxidized form of an aromatic primary amine-based color developing agent.

In the present invention, silver halide is dispersed in a hydrophilic colloid. As such a hydrophilic colloid, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

Preferred examples of the hydrophilic colloid include alkali-treated gelatin most commonly gelatin such as acid-treated gelatin, and a part of this gelatin is converted to phthalated gelatin, derivative gelatin such as phenylcarbamoyl gelatin, albumin, agar, Gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate,
Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone and copolymers of these vinyl compounds can also be used.

The silver halide photographic light-sensitive material of the present invention can contain various known photographic additives. Such examples include, for example, ultraviolet absorbers (for example, benzophenone compounds and benzotriazole compounds), dye image stabilizers (for example, phenol compounds, bisphenol compounds, hydroxychromane compounds, bisspirochroman compounds, hydantoin compounds). Compounds, dialkoxybenzene compounds, etc.), Stein inhibitors (eg, hydroquinone derivatives, etc.), surfactants (eg, sodium alkylnaphthalenesulfonate, naphthalene alkylbenzenesulfonate, sodium alkylsuccinatesulfonate, polyalkylene glycol) ), Water-soluble antiirradiation dyes (for example, azo compounds, styryl compounds, triphenylmethane compounds, oxonol compounds and anthraquinone compounds), hardeners (examples) For example, halogen S-triazine compounds, vinyl sulfone compounds, acryloyl compounds, ethyleneimino compounds, N-methylol compounds, epoxy compounds and water-soluble aluminum salts, etc., film physical property improvers (for example, glycerin, Examples thereof include polyhydric alcohols, polymer dispersions (latex), solid / liquid paraffin, colloidal silica, etc.), optical brighteners (eg, diaminostilbene compounds), and various oil-soluble paints.

As the photographic constituent layers constituting the silver halide photographic light-sensitive material of the present invention, each layer such as an undercoat layer, an intermediate layer, a yellow filter layer, an ultraviolet absorbing layer, a protective layer, and an antihalation layer, in addition to each emulsion layer, It can be appropriately provided as needed.

As a support of the silver halide photographic light-sensitive material of the present invention, a support such as paper, glass, cellulose acetate, cellulose naphthalate, polyester polyamide, or polystyrene, or a support made of paper and a polyolefin (for example, polyethylene and polypropylene) can be used. A laminate of two or more substrates, such as a laminate, can be used as appropriate according to the purpose.

The support is generally subjected to various surface treatments to improve the adhesive to the silver halide emulsion layer, for example, roughening the surface with a mechanical or suitable organic solvent, electron impact treatment, or flame treatment. A surface treatment such as a treatment or an undercoating treatment for providing an undercoating layer can also be used.

The silver halide photographic light-sensitive material of the present invention can form an image by performing a development process known in the art.

As the black and white developing agent used in the present invention,
The Theory of Photographic Process, 4th Edition, by THLames
290-326.

The color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes.

These developers include aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of a salt, for example, the hydrochloride or sulfate, for stability in the free state. These compounds are generally used at a concentration of about 0.1 g to about 30 g for the color developer 1, preferably about 1 g to about 15 g for the color developer 1.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, and 5-amino-2-
Hydroxy-toluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbezen and the like.

Particularly useful primary aromatic amine color developing agents are N, N '
-Dialkyl-p-phenylenediamine compound, wherein the alkyl group and the phenyl group may be substituted with any substituent.

Among them, particularly useful compound examples include N, N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-
p-phenylenediamine hydrochloride, N, N'-dimethyl-p
-Phenylenediamine hydrochloride, 2-amino-5- (N-
Ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-
4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N′-diethylaniline, 4-amino-N- (2-
Methoxyethyl) -N-ethyl-3-methylaniline-
p-Toluenesulfonate and the like can be mentioned.

A known developer component compound can be added to the developer used in the processing of the silver halide light-sensitive material of the present invention, in addition to the above-mentioned developer.

For example, alkali agents such as sodium hydroxide and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners are optionally contained. You can also.

The temperature of the developer is preferably 15 ° C. or higher, generally 20 ° C. to 50 ° C., and for rapid processing, it is also preferable to carry out at 30 ° C. The pH of the developer is usually 7 or higher, most usually about 10-13.

In the practice of the present invention, when a silver halide photographic material containing a high silver chloride emulsion is used as the silver halide emulsion, it is preferable to use a developer containing substantially no bromine ions.

That is, rapid developability is significantly impaired by the presence of bromine ions. The developer containing substantially no bromine ions means a processing solution containing only 1 × 10 ⁻³ mol or less of bromine ions.

High chloride silver halide is partially silver bromide,
It may contain silver iodide. Therefore, when silver bromide is contained, bromine ions are slightly eluted into the developer during development. The eluted bromide ions are partially replaced by halogens in a part other than the image area, that is, due to the difference in solubility of several orders of magnitude between chloride ions and silver in high chloride silver halide which is not developed even in a developing solution. It is also conceivable that it is held in the silver photographic light-sensitive material and taken out to the next step.

However, as described above, although a small amount is obtained by developing a high chloride silver halide, as long as bromine ions can be eluted in the developer, it is impossible to completely maintain the bromine ion concentration in the developer at zero. Can not.

Substantially free of bromine ions means that only bromine ions inevitably mixed, such as bromine ions slightly eluted by development, are not contained, and 1 × 10 ^−3.
The term "mol" indicates the uppermost limit of the concentration of bromine ions unavoidably mixed.

The silver halide photographic light-sensitive material of the present invention contains these color developing agents in the hydrophilic colloid layer as the color developing agents themselves or as precursors thereof, and can be processed by an alkaline activation bath.

The color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and is a Schiff-based precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid iminoxide derivative precursor, a phosphate amide derivative precursor, Sugar amine reactant precursors and urethane type precursors are exemplified.

The precursors of these aromatic primary amine color developing agents are described, for example, in US Pat. Nos. 3,342,599, 2,507,114, and
2,695,234, 3,719,492, British Patent 803,784, JP-A-53-185628, JP-A-54-79035, Research Disclosure No. 15159, 12146
No. 13924.

These aromatic primary amine color developing agents or precursors thereof need to be added so that sufficient color development can be obtained only by the amount thereof when activated.

This amount varies greatly depending on the type of light-sensitive material, but generally ranges from 0.4 mol to 5 mol per mol of silver halide.
Preferably, it is used in the range of 0.5 mol to 3 mol. These color developing agents or precursors thereof can be used alone or in combination.

For incorporation into photosensitive material, it can be added by dissolving in an appropriate solvent such as water, methanol, ethanol, acetone, etc., or emulsified and dispersed using a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. It can be added as a liquid or can be added by impregnating a latex polymer as described in Research Disclosure No. 14850.

When the silver halide photographic light-sensitive material of the present invention is a color light-sensitive material, it is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process.

Many compounds are used as a bleaching agent. Among them, iron (III), cobalt (III), copper (II), etc., polyvalent metal compounds, especially complex salts of these polyvalent metal cations and organic acids, for example, ethylenediaminetetraacetic acid, Nitrilotritriacetic acid, metal complex salts such as aminopolycarboxylic acids such as N-hydroxyethylethylenediamine diacetic acid, malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid or ferricyanates, dichromates, etc. A single or an appropriate combination is used.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, thioether and the like.

After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

The stabilizing solution used for the stabilizing treatment may contain a pH adjuster, a chelating agent, a anti-blur agent and the like. These specific conditions can be referred to JP-A-58-134636 and the like.

The silver halide photographic light-sensitive material of the present invention includes black-and-white or color photographic light-sensitive materials, and is preferably a direct-viewing photographic light-sensitive material that is viewed as a final image, such as black-and-white photographic paper, color photographic paper, and color. Reversal film, color reversal paper, and the like.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. However, this is one embodiment of the present invention, and the present invention is not limited thereto.

Example 1 [Preparation of Silver Halide Emulsion (Em-A to C)] The amounts of additives used in the preparation of the emulsion below are amounts per mol of silver halide unless otherwise specified.

A silver nitrate solution, a solution containing potassium bromide and sodium chloride were tabulated into an inert gelatin aqueous solution by the double jet method.
It was added while keeping the conditions described in 1.

Subsequently, desalting and washing were carried out by a conventional method to prepare silver chlorobromide emulsions Em-A to Em-C, respectively.

Using the above emulsion, sensitized to red sensitivity as shown below, and prepared multilayer silver halide photographic material samples 101 to 112, and performed the following processing, and for each of the sensitivity and residual color contamination as shown below. The stagnation stability was evaluated.

The following seven layers were sequentially coated on a polyethylene resin-coated paper to prepare a multilayer silver halide photographic material sample 101. In addition, the addition amount shown below is an amount per 1 m ² unless otherwise specified.

Layer 1: 1.2 g of gelatin, 0.35 g (in terms of metallic silver, the same applies hereinafter) of a blue-sensitive silver chlorobromide emulsion. An emulsion having an average particle size of 0.8 μm and a silver bromide content of 90 mol% was converted to sodium thiosulfate, By using [D-1], a stabilizer (4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene, hereinafter referred to as [HMT]) is optimally sensitized at 57 ° C. It was prepared by adding. ｝ And 0.9 g of yellow coupler [YC-1] and 0.015 g
2,5-di-t-octylhydroquinone (hereinafter referred to as [HQ-
1]) and dioctyl phthalate (hereinafter referred to as [DOP]).

Layer 2: a layer containing 0.7 g of gelatin and 0.06 of DOP in which HQ-1 is dissolved.

Layer 3: 1.25 g of gelatin, 0.35 g of green-sensitive silver chlorobromide emulsion ｛An emulsion having an average particle size of 0.45 μm and a silver bromide content of 70 mol% was prepared using sodium thiosulfate and a sensitizing dye [D-2]. And 59 ℃
And sensitized optimally by adding a stabilizer ([HMT]). ｝ And DOP obtained by dissolving 0.53 g of the magenta coupler MC-1, 0.12 g of [A-1], 0.2 g of [A-2] and 0.015 g of HQ-1 and 0.01 g of [AI-1]. Containing layer.

Layer 4: a layer having a DOP in which 1.3 g of gelatin, 0.08 g of HQ-1 and 0.5 g of an ultraviolet absorber [UV-1] are dissolved.

Layer 5: 1.4 g of gelatin, 0.3 g of red-sensitive silver chlorobromide @ Em-A
Then, using sodium thiosulfate and chloroauric acid, optimally sensitized at 57 ° C., prepared by adding sensitizing dye [S-1], phenol resin [SS] and HMT as a stabilizer, and 0.3 g
Of cyan coupler [CC-1] and 0.2 g of [CC-2] and 0.02
A layer containing DOP dissolved with g of HQ-1.

Layer 6: 0.14 g of DOP and 0.02 g of [AI-) obtained by dissolving 1.0 g of gelatin and 0.032 g of [HQ-1] and 0.2 g of [UV-1].
2], a layer containing 0.01 g of [AI-3].

Layer 7: Layer containing 0.003 g of silicon dioxide and 0.5 g of gelatin.

[H-1] was used as a hardening agent in an amount of 5 mg / g of gelatin, [H
-2] was added in an amount of 10 mg / g of gelatin.

Further, Samples 102 to 112 were prepared in the same manner except that a sensitizing dye was added in the preparation of Sample 101 as shown in Table-2.

The following evaluation was performed about the obtained sample.

(1) Evaluation of Sensitivity Each sample was subjected to red separation exposure using a sensitometer KS type (manufactured by Konica) and processed according to the processing steps described below. After the treatment, sensitometric measurement was performed with a PDA-65 type densitometer (manufactured by Konica). Table 2 shows the results.
Is shown as a relative sensitivity when is set to 100. The larger this value is, the better.

(2) Evaluation of residual color contamination pressure Each sample was processed in the unprocessed state according to the processing steps described below, using a Hitachi spectrophotometer Model U-3410 and an uncoated polyethylene resin-coated paper support as a control. Was determined from the area of absorption caused by Table 2 shows the results.
It is shown as a relative area when 1 is set to 100. The smaller this value is, the better.

(3) Evaluation of stagnation stability After the emulsion was prepared, it was kept at 50 ° C. for 6 hours, and the sample was evaluated in the same manner as in the above (1). The results are shown in Table 2 in terms of relative sensitivity when the sample immediately coated without preservation after preparation of the emulsion was taken as 100. The larger this value is, the better.

(Coloring process)

 [1] Color development 38 ° C for 3 minutes and 30 seconds [2] Bleaching and fixing 33 ° C for 1 minute and 30 seconds [3] Washing treatment 25 ° C to 30 ° C for 3 minutes [4] Drying 75 ° C to 80 ° C for about 2 minutes [Processing solution Composition] (Color developing solution) Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino -N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.5 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g And adjust the pH to 10.20.

(Bleach-fixing solution) Ethylenediaminetetraacetate ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid. , Add water to make the total amount 1 As is clear from Table 2, the sample using the sensitizing dye of the present invention has high sensitivity, improved residual color contamination, and excellent stagnation stability.

Example 2 In the same manner as in Example 1, the following seven layers were sequentially coated on a polyethylene resin-coated paper to prepare a silver halide photographic material 201 having rapid processing compatibility.

H-1 shown in Example 1 was used as a hardener.

Each color-sensitive emulsion was prepared as follows.

The blue-sensitive silver chlorobromide emulsion Em-C was optimally sensitized at 57 ° C. using sodium thiosulfate and a sensitizing dye (D-1), and a stabilizer (SB-1) was added.

The green-sensitive silver chlorobromide emulsion Em-B was optimally sensitized at 59 ° C using sodium thiosulfate and a sensitizing dye (D-2), and a stabilizer (SB-1) was added.

Red-sensitive silver chlorobromide emulsion Em-B was optimally sensitized at 60 ° C. using sodium thiosulfate, sensitizing dye (S-1) and phenol resin, and a stabilizer (SB-1) was added. .

Samples 202 to 212 were prepared in the same manner except that the sensitizing dye (S-1) of the red-sensitive emulsion of Sample 201 was changed as shown in Table-3.

This sample was evaluated for relative sensitivity, residual color contamination, and stagnant stability in the same manner as in Example 1. The processing was performed according to the following processing steps.

<Processing step> Processing temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds (Color developing solution) Pure water 800ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid Disodium 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate Add 27 g water to bring the total volume to 1 and adjust to pH = 10.10.

(Bleach-fixing solution) Ethylenediaminetetraacetate ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 and add potassium carbonate or Adjust to pH = 5.7 with glacial acetic acid.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% Aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Add water to make the total amount 1 and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

 Table 3 shows the obtained results.

As is evident from Table 3, even when rapid processing was performed using a silver chloride emulsion, the sample using the sensitizing dye of the present invention had high sensitivity, improved residual color contamination, and reduced stagnation safety. It turns out that it is excellent.

Example 3 The hardener of Example 2 was replaced with bis (vinylsulfonylmethyl)
A sample was prepared in the same manner as in Example 2 except that the sample was changed to ether. For these, the same tests as in Example 2 were performed, and it was confirmed that the effects of the present invention were obtained.

〔The invention's effect〕

As described in detail above, by using the specific sensitizing dye represented by the general formula [I] as in the present invention, a silver halide having high sensitivity, little residual color contamination and excellent stagnation safety can be obtained. A photographic light-sensitive material can be provided.

Claims (1)

(57) [Claims] 1. The method according to claim 1, wherein at least one layer of silver halide is provided on a support.
In a silver halide photographic light-sensitive material containing an emulsion layer,
At least one of the silver halide emulsion layers has the following general formula
Spectral enhancement by at least one of the dyes represented by [1]
Halo characterized by containing sensed silver halide grains
Silver gemide photographic material. General formula [I](Where R₁Is an alkyl group or -J_Two-C≡CH, J₁
And J_TwoRepresents a divalent linking group. R_Two, R_Three, R_Four, R_Five, R₆, R₇,
R₈, R₉Is hydrogen atom, alkyl group, aryl group, halogen
Atom, represents an alkoxy group, R_Two~ R_FiveAnd R₆~ R₉Is
A ring may be formed in cooperation with each adjacent substituent.
Z is a group of hydrocarbon atoms necessary to form a 5- or 6-membered ring
Represents X Represents an acid anion. l represents 0 or 1
You. ]